Adducts of decachlorooctahydro-1, 3, 4-metheno-2h-cyclobuta (cd) pentalen-2-one with amines and alcohols



United States Patent 3,240,808 ADDUCTS OF DECACHLOROOCTAHYDRO-l,3,4-

METHENO 2H CYCLOBUTA(cd) PENTALEN-Z. ONE WITH AMINES AND ALCOHOLSEverett E. Gilbert, Morris Township, Morris County, and

3,240,808 Patented Mar. 15, 1966 hydroxy alcohols, secondary monohydroxyalcohols, primary monoamines and secondary monoamines. The alcohols andamines may be aliphatic, cycloaliphatic or aromatic and may containsubstituents such as alkyl or aryl groups, ether or thioether linkagesand halogens. Pasquale Lomhardo East Hanover Township Morris 5 County,N.J., assignors to Allied Chemical Corporation, f f; intended that t eterm primary mono- New York, N.Y. a corporation of New York amlneslnclude ammonia. Typical reactions within the N D i il O 31, 19 1, sa 14scope of the invention may be represented as follows:

6 Claims. (Cl. 260563) (1) Alcohol Adducts 01 C1 C1 C1 R 1 (:1 c ROH C1c1 (2) Amine Adducts l on :1 C C1 C1 HR 01 C C1 01 Cl p1 0 01 1 gg (:1 IC1 C1 An object of the present invention is to provide new ketoneadducts exhibiting unusually high epesticidal activity.

Another object of the invention is to provide new pesticidalcompositions containing ketone adducts as active ingredients.

Yet another object of the present invention is to provide a method ofcombatting pests comprising contacting the pests with new pesticidalcompositions containing ketone adducts as active ingredients.

Other objects and advantages of the present invention will be apparentfrom the following description.

The ketone adducts contemplated by this invention comprise thoseobtained by reacting anhydrous ketone with a member of the groupconsisting of primary mono- If the ketone 1 available in hydrated form,it can be dehydrated by heating it in an oven at temperature of about135 to 150 C. or by refluxing it with an aromatic solvent such as xyleneto remove the Water. The water can also be removed by adding an excessof the alcohol or amine followed by distillation to remove the water andexcess alcohol or amine.

If desired, the reaction of ketone with alcohol or amine may be carriedout in the presence of an inert solvent, preferably an aliphatic oraromatic hydrocarbon or chlorinated hydrocarbon such as chloroform,xylene, toluene, benzene, hexane, petroleum ether, methylene chloride,etc.

Although we prefer to use at least a stoichiometric amount of thealcohol or amine, the desired adduct may be prepared using lower amountsof the alcohol or amine, e.g. down to about 0.25 mol of the alcohol oramine per mol of ketone. In such case, the reaction productcomprises'the adduct in admixture with unreacted ketone. If astoichiometric excess of the alcohol or amine is used, the excess can beremoved by distillation.

The reaction is carried out at temperature varying from about 40 to 150C. Preferably, the temperature employed is about 100 C. in the absenceof an inert solvent.

The following examples are typical of preparation of the ketone adductsof this invention. In the examples parts are by Weight:

EXAMPLE 1 18 parts of purified .ket-one hydrate (4 mols water) weremixed with 2.8 parts of Pentasol No. 27 (consisting predominantly of amixture of primary and secondary amyl alcohols), the amount of alcoholbeing equimolecul-ar to that of the ketone. The mixture was heated at100 C. for one hour, then at -5 C. for two hours. Heat and vacuum werethen applied to remove the water formed. A dark viscous oil resultedwhich solidified on cooling. Infrared analysis showed that substantiallyall of the ketone had reacted.

3 EXAMPLE 2 The procedure of Example 1 was employed, using 18 parts ofpurified ketone hydrate and an equimolecular amount (3.2 parts) ofn-hexylamine. The product was a viscous oil which solidified to a waxysolid on cooling. Infrared analysis showed the .product to be the adductof ketone and n-hexylamine, as evidenced by nitrogenhydrogen andhydroxyl stretching and the absence of carbonyl absorption.

EXAMPLE 3 The procedure of Example 1 was followed, using 18 parts ofketone hydrate and an equimolecular amount (5.9 parts) ofn-dodecylamine, except that the two hour heating at 100i5 C. wasomitted. The liquid product solidified on cooling to a waxy solid.Infrared analysis showed the product to be the adduct of ketone andn-dodecylamine, as evidenced by nitrogen-hydrogen and hydroxylstretching and the absence of carbonyl absorption.

Purified adducts of ketone and n-butanol, n-hexylamine and aniline wereprepared by recrystallization from petroleum ether (30-60 C.). Theresulting purified products possessed the following melting points:

Degrees/Centigrade n-Butanol adduct 162-5 n-Hexylarnine adduct 57-9Aniline adduct 161-2 Infrared spectra of the adducts differedsignificantly from that of ketone. All three of the adducts showedhydroxyl stretching at 2.78 microns but no carbonyl absorption. Allthree adducts showed carbon-hydrogen stretching, the n-butanol adduct at3.35 and 3.46 microns, the nhexylamine adduct at 3.39 and 3.47 micronsand the aniline adduct at 3.28 microns. In addition, the n-hexylamineadduct showed nitrogen-hydrogen stretching at 2.96 microns, and theaniline adduct showed the same stretching at 2.92 microns. The anilineadduct also showed aromatic ring vibrations at 6.24, 6.61, 6.68 and 6.97microns.

The adducts of this invention may be applied as pesticides as is but areadvantageously incorporated as active ingredients in suitable liquid orsolid carriers to provide pesticidal spray or dust compositions. Theadducts include those derived from (1) alkyl, monocyclic arylsubstitutedalkyl and cycloalkyl-substituted alkyl primary and secondary monohydricalcohols containing from 4 to 12 carbon atoms, (2) cycloalkyl andalkyl-substituted cycloalkyl secondary monohydric alcohols containingfrom 4 to 12 carbon atoms, (3) alkyl, monocyclic aryl-substituted alkyl,cycloalkyl-substituted alkyl and cycloalkyl primary and secondarymonoamines containing from 4 to 12 carbon atoms, (4) monocyclic aryl andalkyl-substituted monocyclic aryl primary monoamines containing from 4to 12 carbon atoms, (5) condensates of one mole of an alkyl-substitutedphenol in which the alkyl contains up to 9 carbon atoms, a lower alkylprimary monohydric alcohol or a lower alkyl primary or secondarymonoamine with one to four mols of ethylene oxide or propylene oxide,(6) furfurylamine and (7) piperidine.

In particular, we have found that when the alcohol or amine usedcontains from 4 to 12 carbon atoms, the resulting adducts haveexceptionally high toxicity toward pests, including insects and fungi.Accordingly, provision of these adducts constitutes a specificembodiment of this invention.

We have also discovered that the adducts of this invention havesubstantially greater solubility in aromatic solvents than ketone,producing stable solutions of at least about 12% and usually at leastabout 20% concentration. Moreover, the resulting liquid compositionshave far greater resistance to the effect of moisture than liquid ketonecompositions.

We have discovered further that wettable powder compositions containingthe adducts of this invention, unlike conventional wettable powdercompositions of ketone, are unaffected by moisture and do not cake instorage.

The liquid pesticidal compositions generally contain in proportions byweight about 10 to 25% of the ketone adduct as active ingredient, about65 to 88% of an aromatic solvent and about 2 to 10% of a suitablewetting or emulsifying agent, such as diglycol oleate, p-isooctyl phenylether of polyethylene glycol, blends of alkyl aryl polyether alcoholswith alkyl aryl sulfonates and blends of polyoxyethylene sorbitan estersof mixed fatty and resin acids with alkyl aryl sulfonates. The resultingconcentrate solution is diluted or admixed with water to form an aqueousdispersion or emulsion suitable for spray application containing about0.001 to 0.1% by weight of ketone adduct.

Representative aromatic solvents which may be used in preparing theliquid pesticidal compositions include xylene, high aromatic solvents,methylated naphthalenes, heavy aromatic naphtha, etc.

The wettable powder compositions generally contain in proportions byweight about 25 to 75% of the ketone adduct as active ingredient, about20 to 73% of a finely divided solid carrier and about 2 to 5% ofsuitable wetting and dispersing agents. Typical wetting agents includepolyether sulfonates, alkyl aryl sulfonates, etc. Typical dispersingagents include ligninsulfonates, naphthalene sulfonic acid-formaldehydecondensates, etc.

The wettable powder compositions can readily be prepared by mixing ormilling the ketone adduct with the carrier and wetting agent to atypical particle size of from about 3 to 40 microns. The composition isadmixed with water to form an aqueous dispersion suitable for sprayingcontaining about 0.001 to 0.1% by weight of ketone adduct.

Representative solid carriers which may be used in preparing thewettable powders include magnesium and aluminum silicates (talc, kaolinclays, attapulgite clays, etc.), carbonates (dolomite, chalk, etc.),materials containing silicic acid (diatomaceous earth), fullers earth,gypsum, sulfur, etc.

The dosage of the adducts employed depends on the particular organismsto be controlled, field conditions, etc. as known in the art. In anyevent, sufficient quantities of the adducts are used to provide thedesired toxicity.

As shown in the tests given below, ketone adducts formed from thealcohols and amines containing 4 to 12 carbon atoms are generally moretoxic than ketone to insects and/or fungi. 'The adducts were prepared byreacting anhydrous ketone with an equivalent molar amount of the alcoholor amine. The anhydrous ketone was obtained by dissolving hydratedketone (3-4 mols water) in xylene and removing the water by azeotroping.

1% acetone solutions of the adduct or ketone, diluted with varyingquantities of water, were tested against spores of Sclerotz'niafructicola (brown rot of stone fruits), produced by growing the funguson potato dextrose agar plants for one week. Following an incubationperiod of 24 hours at 65 F., the solutions were examined under amicroscope to determine average percent germination of spores at eachconcentration.

Texts on toxicity to pea aphids (Macrosiphum pisi). were carried out byremoving the pea aphids from infested plants, placing them on a Wirescreen and spraying them with a formulation of the adduct or ketone.Following treatment, the pea aphids were confined to untreated broadbean plants. Record of kill was made three day after treatment. Theformulation used comprised (by volume) 1 part of the adduct or ketone(as an acetone solution comprising 4.8 grams of the adduct or ketone per100 cc. of solution) per 39 parts acetone plus 40 parts Water.

Tests on toxicity to Mexican bean beetle larvae (Epilachna varivestis)were carried out by spraying horticultural (cranberry) bean plants witha formulation of the adduct or ketone and allowing the plants to dry.The larvae were confined to the treated foliage by means of wire cages.Record of kill was made three days after treatment. The formulation wasprepared by diluting (by volume) one part of the adduct or ketone (as anacetone solution comprising 4.8 grams of the adduct or ketone per 100cc. of solution) with 319 parts of water.

Tests on Southern armyworms (Prodenia eridania) were carried out byspraying horticultural (cranberry) bean plants with a formulation of theadduct or ketone and allowing the plants to dry. The armyworms wereconfined to the treated foliage by means of wire cages. Mortality countwas made three days after treatment. The formulation was prepared bydiluting (by volume) one part of the adduct or ketone (as an acetonesolution comprising 4.8 grams of the adduct or ketone per 100 cc. ofsolution) with 639 parts of Water.

TABLE II Percent kill Sample Toxicity to Toxicity t pea aphids Mexicanbean beetle larvae Toxicity to southern armyworms KetoneMixed primaryamyl alcohols adduct KetoneMixed branched chain primary amyl alcoholsadduct Ketone-Aniline adduct Ket0ne-Cyclohexylamine adductKetone-n-Hexylamine ad 11 100 Ketonkn-Dodecylamme adductKetoneCondensate of nonyl phenol and 4 ethylene oxide adductKetone-Condensate of nbutylamine and 4-ethylene oxide adductKetone1-butancl adduct Ketone 0 Many other adducts of the alcohols andamines containing from 4 to 12 carbon atoms exhibit insecticidal and/orfungicidal activity greater than that of ketone, including those listedin Table III.

Although the particular ketone adducts described above exhibit unusuallyhigh insecticidal and/or fungicidal activity, any adduct obtained byreacting anhydrous ketone with a member of the group consisting ofprimary monohydroxy alcohols, secondary monohydroxy alcohols, primarymonoamines and secondary monoamines may constitute the active ingredientin compositions of varying degrees of pesticidal activity.

As indicated above, we have found that the adducts may be prepared ashigher strength liquid pesticidal compositions in aromatic solvents thanketone. At the same time these compositions have greater stability tomoisture. Moreover, many of the liquid compositions are more easilyemulsifiable in water than ketone. In preparing the liquid compositionsthe adducts obtained from primary amyl alcohols are preferred since theprimary amyl alcohols are cheap and meet all of the objectives set forthabove.

The table set forth below shows solubility and emulsification tests onadducts of this invention. Three'types of solubility tests were run:

In Test A, indicates no separation on standing 24 hours at roomtemperature as a 2530% solution (6 grams anhydrous ketone, 18 gramsxylene and 1 molecular equivalent of adducting compound (alcohol oramine)). indicates separation under these conditions.

In Test B, indicates no separation of the above solution on standing 24hours at 18 C. indicates separation under these conditions. A blankindicates no test was made.

In Test C, indicates no separation on standing 24 hours at -l8 C. from a40% solution. indicates separation under these conditions. A blankindicates no test was made.

In the emulsification test, 9 grams of the solution from solubility TestA was mixed with one gram Atlox 2081' (an emulsifier comprising a blendof polyoxyethylene sorbitan esters of mixed fatty and resin acids withan alkyl aryl sulfonate). 2 cc. of this solution was added to 98 cc. ofhard water (342 ppm.) in a glass-stoppered 100 cc. graduated cylinderwhich was immediately inverted twice. A smooth emulsion was formed ifthe mixture successfully passed the test. Passing samples were theninverted 30 more times and allowed to stand undisturbed for one hour. Nooil or not more than 1 cc. of cream could separate at the bottom or topof the cylinder during this TABLE III Solubility tests Adductingcompound Emulsification test Methanol l-pentanol t Primary amyl cohol 3pentanol 2-methyl-1-butanol Cyclopentanol lltllllllll llilllllllll-heptanol 3-methylcyclohexanol. Methyl cyclopentyl carbinol- Cyclohexylmethanol Benzyl alcohol Phenethyl alcohol- Methyl benzyl alcohol-decanol 2-seo-butybcyclohexanoh. 2,6,8-trimethyl-4-nonanol2-cyclohexyl-cyclohexanol. l oetadecanol Dirnethylamine. n-Propylamine,Isopropylamine.

llllllllll llllllilllll :Illlllllllllllllllllll l l 1+++| 1++| r ln-Arnylamine. Furturylamine. Piperidine Aniline n-HeptylamineBenzylamine o-Toluidine. n-0 ctylamine- 2 ethylhexylamir1en-Methylbenzylamine or-P heny1ethylamine Di-sec-butylamine DodecylamineTetradecylamine Hexadecylamine Dihydroabietylamine Condensate ofmethanol and ethylene oxide TABLE III-Continued Solubility testsAddueting compound Emulslfication test. A B C Condensate of ethanol andethylene oxide Condensate of nonyl phenol and ethylene oxide Condensateof n-ethyl aniline and ethylene oxide Condensate of di-(n-butyl) aminoand ethylene oxide Condensate of diethylamine and ethylene oxideCondensate of n-butylamine and ethylene oxide Condensate of di-(n-butyl)amine and propylene oxide Condensate of ammonia and propylene oxide Inmaking the liquid compositions of this invention, it is preferred to usealcohols and amines derived from hydrocarbons. The alcohols preferablycontain from 1 to 18 carbon atoms while the amines preferably containfrom 1 to 20 carbon atoms. As shown in the table above, various oxiranecondensates which are primary alcohols may also be used although none ofthem is derived from a hydrocarbon.

The following wettable powder pesticidal compositions are typical ofthose contemplated by the present invention.

The following emulsifiable concentrate pesticidal compositions aretypical of those contemplated by the present invention.

Sample #1 Sample #3 (wt. percent) Sample #2 (wt. percent) Adduet ofketone and "Pentasol 2 Adduct of ketone and n-hexylamine Adduct ofketone and n-dodecylamine- Xylene Toximul R (an emulsifier comprisng ablend of an alkyl aryl polyether alcohol with an alkyl aryl sulfonate)Atlox G8916DJI3300 (an emulsifier comprising a blend of polyoxyethylenesorbitan esters of mixed fatty and resin acids with an alkyl arylsulfonate) Gil Since various changes and modifications may be made :inthis invention without departing from the spirit thereof, the inventionis deemed to be limited only by the scope of the appended claims.

We claim:

1. An adduct of decachlorooclahydro-l,3,4-metheno- ZH-cyclobuta (cd)pentalen-Z-one and a member of the group consisting of (1) alkyl,monocyclic aryl-substituted alkyl and cycloalkyl-substituted alkylprimary and sec- 'ondary monohydric alcohols containing from 4 to 12carbon atoms, (2) cycloalkyl and alkyl-substituted cycloalkyl secondarymonohydric alcohols containing from 4 to 12 carbon atoms, (3) alkyl,monocyclic aryl-substituted alkyl, cycloalkyl-substituted alkyl andcycloalkyl primary and secondary monoamines containing from 4 to 12carbon atoms, (4) monocyclic aryl and alkyl-substituted monocyclic arylprimary monoamines containing from 4 to 12 carbon atoms, (5) condensatesof one mol of a member of the group consisting of alkyl-substitutedphenols in which the alkyl contains up to 9 carbon atoms, lower alkylprimary monohydric alcohols and lower alkyl primary and secondarymonoamines with one to four mols of a member of the group consisting ofethylene oxide and propylene oxide, (6) furfurylamine and (7)piperidine. I

2. An adduct of decachlorooctahydro-l,3,4-metheno- 2H-cyclobuta (cd)pentalen-Z-one and an alkyl primary monohydric alcohol containing from 4to 12 carbon atoms.

3. An adduct of decachlorooctahydro-1,3,4-metheno- 2I-I-cyclobuta (cd)pentalen-Z-one and a primary amyl alcohol.

4. An adduct of decachlorooctahydro-l,3,4-metheno- 2H-cyclobuta (cd)pentalen-Z-one and l-decanol.

5. An adduct of decachlorooctahydro-1,3,4-metheno- 2H-cyclobuta (cd)pentalen-Z-one and an alkyl primary monoamine containing from 4 to 12carbon atoms.

6. An adduct of decachlorooctahydro-1,3,4-metheno- 2H-cyclobuta (cd)pentalen-Z-one and n-dodecylamine.

References Cited by the Examiner UNITED STATES PATENTS 2,635,979 4/1953Lidov 260-563 X 2,829,147 4/1958 Molotsky et a1. 260343.2 2,872,3672/1959 Haynes et al. 16730 2,883,425 4/1959 Kealy 260-586 2,943,0166/1960 Rosen et al. 16730 2,995,606 8/1961 Molotsky 260-586 3,055,9489/1962 Hoch et al. 260-611 3,096,239 7/1963 Hoch et al. 260-563 X OTHERREFERENCES McBee, et al.: J. Am. Chem. Soc., vol. 78, pages 1511 to1512, 1956.

CHARLES B. PARKER, Primary Examiner.

FRANK CACCIAPAGLIA, JR., JULIAN S. LEVITT,

Examiners.

1. AN ADDUCT OF DECACHLOROOCTAHYDRO-1,3,4-METHENO2H-CYCLOBUTA (CD)PENTALEN-2-ONE AND A MEMBER OF THE GROUP CONSISTING OF (1) ALKYL,MONOCYCLIC ARYL-SUBSTITUTED ALKYL AND CYCLOALKYL-SUBSTITUTED ALKYLPRIMARY AND SECONDARY MONOHYDRIC ALCOHOLS CONTAINING FROM 4 TO 12 CARBONATOMS, (2) CYCLOALKYL AND ALKYL-SUBSTITUTED CYCLOALKYL SECONDARYMONOHYDRIC ALCOHOLS CONTAINING FROM 4 TO 12 CARBON ATOMS, (3) ALKYL,MONOCYCLIC ARYL-SUBSTITUTED ALKYL, CYCLOALKYL-SUBSTITUTED ALKYL ANDCYCLOALKYL PRIMARY AND SECONDARY MONOAMINES CONTAINING FROM 4 TO 12CARBON ATOMS, (4) MONOCYCLIC ARYL AND ALKYL-SUBSTITUTED MONOCYCLIC ARYLPRIMARY MONOAMINES CONTAINING FROM 4 TO 12 CARBON ATOMS, (5) CONDENSATESOF ONE MOL OF A MEMBER OF THE GROUP CONSISTING OF ALKYL-SUBSTITUTEDPHENOLS IN WHICH THE ALKYL CONTAINS UP TO 9 CARBON ATOMS, LOWER ALKYLPRIMARY MONOHYDRIC ALCOHOLS AND LOWER ALKYL PRIMARY AND SECONDARYMONOAMINES WITH ONE TO FOUR MOLS OF A MEMBER OF THE GROUP CONSISTING OFETHYLENE OXIDE AND PROPYLENE OXIDE, (6) FURFURYLAMINE AND (7)PIPERIDINE.